Developing unit with member for regulating quantity of developer.

Abstract: The present invention relates to a member for regulating the quantity of a developer that is free from deterioration in the physical properties thereof even if the same is used for a long time, the member for regulating the quantity of a developer being made of a polyurethane rubber composition which contains an amine-type catalyst.

Description: The present invention relates to a developing unit including a regulatory member for regulating the quantity of developer used to develop an electrostatic latent image formed on an image carrying member so as to form a visible image. It also relates to copying machines and laser beam printers including such a developing unit. It also concerns a method of developing an electrostatic latent image and a method of producing a printed image. Related Background Art A developing unit, as shown in Fig. 2, comprises an electrophotographic photosensitive member 1; a developer carrying member 3 (hereinafter a "developing sleeve") attached to a developer container 2 and disposed at a predetermined distance from the electrophotographic photosensitive member 1; a blade 4 (hereinafter an "elastic blade") for regulating the quantity of the developer; an elastic roller 5; and a one-component developer 6 (hereinafter "toner"). As a means for reducing the thickness of a toner layer, which is carried by the developing sleeve to the developing portion, a structure has been known in which the elastic blade is brought into contact with the developing sleeve to regulate the toner, which is allowed to pass through between the elastic blade and the developing sleeve, to form a thin layer of toner on the developing sleeve; and electricity charged frictionally (triboelectricity) for forming a latent image is supplied to the toner in the contact portion between the elastic blade and the developing sleeve. Since distribution of the size of toner particles ranges from several µm (microns) to ten and several µm (microns) in the toner layer formed on the developing sleeve, the development using the elastic blade is required to accurately bring the elastic blade to the top end of the surface of the developing sleeve, to frictionally charge electricity to the toner held between the developing sleeve and the elastic blade and to form a uniform thin layer on the developing sleeve. As a member for regulating the quantity of the developer, a rubber member 14 or a member 7 manufactured by integrating a supporting member 7a made of metal foil or a plastic sheet and a rubber member 7b has been used. As the rubber member, a urethane rubber elastic member for regulating the quantity of a developer has used. As the urethane rubber member, adipate urethane rubber containing polyester polyol as the molecular skeleton thereof has been mainly used in terms of the wear resistance, low plasticity deformability and frictional electricity charging easiness. However, a hydrolyzing reaction proceeds in the member for regulating the quantity of a developer using urethane rubber as time passes due to water in the air, causing the physical properties to deteriorate. Such deterioration leads to a fact that the pressure of the member for regulating the quantity of a developer to press the developing sleeve is lowered and, therefore, the set pressure level is changed undesirably or the area of contact is changed due to the deterioration in the hardness of the rubber. Thus, the easiness to form the thin layer and that of frictionally charging electricity deteriorate. An apparatus for developing an electrostatic latent image formed on the image carrying member to obtain a visible image, for example, a copying machine or a laser beam printer, encounters excessive rise in the temperature therein to about 40°C and lowering in the temperature to the ambient temperature after the operation of the apparatus has been stopped. Therefore, dew condensation takes place repeatedly by a degree corresponding to the ambient humidity while subjecting the urethane elastic blade to a similar condition. Thus, the quality of the developed image is affected considerably by the deterioration occurring due to hydrolyzing reaction caused from the contact with water taking place in accordance with the temperature, humidity and the period of use. In particular, the adipate urethane rubber containing polyester polyol as the molecular skeleton thereof has excellent characteristics exemplified by the wear resistance as compared with polyether polyol. However, the adipate urethane rubber containing the ester group that has poor resistance against hydrolysis encounters change in the molecular structure of urethane rubber, causing its initial mechanical characteristics to deteriorate such that the mechanical characteristics deteriorates rapidly in an exponential function manner due to factors, such as time, temperature and humidity. As a result, use of the adipate urethane rubber for a long time under a certain environment causes the hardness of the rubber to be changed and plastic deformation to take place due to deterioration in the mechanical characteristics. Thus, the reduction in the contact pressure with the developing sleeve deteriorates the easiness to form a thin layer and the frictionally charging characteristics. What is worse, the deterioration further increases the viscosity of the rubber, causing a problem to occur such that the rubber adheres to the developing sleeve or the toner. Accordingly, suggestions have been made to use a hydrolysis prevention material capable of preventing hydrolysis of the urethane rubber and to use an antioxidant to prevent deterioration in the urethane rubber due to heat. However, a desire for reducing the cost of the elastic blade made of urethane rubber and improving manufacturing yield raises a necessity of improving the urethane molding easiness and, thus, a catalyst capable of enhancing the reaction must be used in a considerably large quantity. The catalyst undesirably enhances the hydrolysis, thus causing a problem to take place in that satisfactory quality cannot be obtained and the period, in which the urethane blade can be used, cannot be lengthened. SUMMARY OF THE INVENTION A problem with which the invention is concerned is therefore to provide a developing unit having an improved regulatory member for regulating the quantity of developer which is allowed to pass between said regulatory member and a developing sleeve of the unit. The present invention provides a developing unit as defined in claim 1, a copying machine or a laser beam printer incorporating the same, and methods of developing an electrostatic latent image and of producing a printed image using the same. Use of the above regulatory member for regulating the quantity of a developer enables deterioration in the physical properties occurring due to hydrolysis to be prevented, and the developing performance can be maintained. In addition, the member for regulating the quantity of a developer can be used for a long time and, thus, the cost of which can be reduced and the manufacturing yield of which can be improved. In order to raise the molding velocity of the urethane rubber, a method of increasing the quantity of the catalyst has been employed usually. As the catalyst for enhancing the reaction of the urethane rubber, an amine type catalyst, such as triethylene diamine or tetramethylguanidine, is used or they are used mixedly. The amine-type catalyst has an advantage that it can easily handled because the reaction speed is relatively constant with respect to scattering of the quantity of addition. The relationship between the catalyst and the hydrolysis characteristics was examined in such a manner that the elastic blade made of urethane was mounted on a developing unit and the unit is mounted on a laser beam printer to be tested in an ambient that the temperature was 32.5°C and the relative humidity was 90%, resulting in that the amine type catalyst exhibited excellent characteristics. Other and further objects, features and advantages of the invention will be evident from the following detailed description of the preferred embodiments in conjunction with the attached drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view of explanatory showing the shape of a blade member for regulating the quantity of a developer; and Fig. 2 is a diagram which illustrates a developing unit using the member for regulating the quantity of a developer. DESCRIPTION OF THE PREFERRED EMBODIMENTS As the amine reactive catalyst, it is preferable to use an amine-type catalyst exemplified by triethylene diamine, tetramethyl guanidine, pentamethyl diethylene triamine, dimethyl imidazole and tetramethyl propane diamine in terms of improving the resistance against hydrolytic reaction. In particular, it is preferable to use triethylene amine or pentamethyl diethylene triamine. The elastic blade made of urethane can be manufactured by, for example, a pre-polymer method which has the steps of causing excess polyisocyanate and polyol to react with each other to prepare a prepolymer in which an end of the polyol contains an isocyanate group or a prepolymer in which the end contains non-reacted and, thus, free polyisocyanate; and causing polyol serving as a linking material to react with the prepolymer. A preferred polyisocyanate component is exemplified by 2,4-toluenediisocyanate (TDI), its isomer, their mixture; diphenylmethane-4,4'-diisocyanate (MDI), polymethylene polyphenyl polycyanate (polymeric-MID), carbodiimide denatured diphenylmethane-4,4'-diisocyanate, hydrogenated MDI, 1, 5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate, a system in which multifunctionated and denatured polyisocyanate or the like is used, for example, a system to which branched or pre-supplied trimethylol propane denatured diphenyl methane-4,4'-diisocyanate is added, or a system in which diphenylmethane-4,4'-diisocyanate denatured by a chain extending material, such as 1,4-butane diol, is added to the polyisocyante component. In particular, it is preferable to employ diphenylmethane-4,4'-diisocyanate material in terms of securing safety (demulcent characteristics) of the working environment and easiness of reaction control. The polyol component for use in the present invention is a mixture of compounds of long-chain polyol serving as the main chain component, a short-chain two-function compound serving as the chain extending component and three or more functional compound serving as the linking material. A preferred main-chain component of the polyol is exemplified by ethylene adipate polyester polyol or butylene adipate polyester polyol, each of which can be prepared from a dibasic acid and a polyalcohol; ethylene butylene adipate type polyester polyol obtainable from a combination of one or more kinds of dibasic acids and one or more kinds of polyalcohols; polylactone-type polyester polyol prepared from a ring-opening reaction of a lactone compound; an acryl compound of their polyol components; denatured polyol obtainable from a silicon compound or a fluorine compound; and a variety of the aforesaid polyol compounds. The allowable main-chain component is not limited to the polyester-type polyol. For example, polycarbonate-type polyol, polypropylene-type polyether polyol, polyethylene-type polyether polyol, polytetramethylene-type polyether polyol or a copolymer polyether-type polyol may be employed. As the chain extending component, it is preferable to employ a dibasic amine compound, such as 3,3'-dichloro-4,4'-diaminodiphenylmethane or 4,4'-diaminodiphenyl methane; or a dihydroxy compound, such as ethylene glycol, 1,4-butane diol, bis(β-hydroxyethyl) hydroquione ether or polyethylene glycol. As the linking material, it is preferable to employ three or more function compound (glycerin or trimethylol propane). If necessary, a material capable of preventing hydrolysis is added to the polyurethane rubber composition. As the material for preventing hydrolysis, it is effective to add any one of a material selected from a group consisting of a carbodiimide compound, 4-t-butyl catechol, azodicarbonamide, azodicarboxylic ester and aliphatic amide. In particular, it is preferable to employ Stabaxol-1 or P or P-100 (each of which is trade name of Bayer) which is a carbodimide-type material in a quantity of 1 wt% or less. If necessary, an anti-oxidant is added to the polyurethane rubber composition. As the anti-oxidant, a phenol or amine type anti-oxidant may be employed. It is preferable that the phenol-type anti-oxidant be employed to prevent contamination of the member for carrying the developer and the toner. In particular, it is preferable to employ a hindered phenol type, polymeric and non-transfer type anti-oxidant. For example, it is preferable to use Irganox 1010 or 1035 or 1076 (trade name of Nihon Chibaguiki) in a quantity of 1 wt% or less. As for the hardness of the rubber in the elastic blade, if the rubber is too soft, the area of contact (nip) between the developing sleeve and the elastic blade affecting the easiness to charge the toner with frictional electricity is enlarged excessively. Therefore, the lubricity deteriorates, thus causing the irregular density to take place. Therefore, it is preferable that the JISA hardness be 50° or higher. If the rubber is too hard, the area of contact is reduced, thus causing the frictional charge to be inhibited. In this case, irregular density takes place or undesirable lines appear. Therefore, it is preferable that the JISA hardness be 80° or lower, and more preferably 60° to 70°. If the compression set (JIS K6301) takes place excessively in the elastic blade, irreversible deformation occurring due to plastic flow in the rubber with respect to the contact pressure, that is, creep takes place if the elastic blade is in contact with the developing sleeve for a long time. Thus, the contact area increases in accordance with the diameter of the cylindrical developing sleeve, causing a problem of irregular density to arise. If only the rubber elastic member is used to form the elastic blade, the contact pressure is reduced due to the creep. Therefore, irregular thickness of the toner applied to the developing sleeve takes place or blooming occurs in which a full white portion is undesirably formed when a solid black image is intended to be output on paper due to unsatisfactory frictional charge with electricity. As a result, it is preferable that the compression set be 20% or less, and more preferably 10% or less. Examples and comparative examples of the present invention will now be described. Examples Example 1 Rubber ethylene adipate type urethane polymer (PEA) (Mn1500 manufactured by Nihon PolyUrethane, NCO 6.2 wt%) 100g Hardening Material 1,4-butandiol 3.9 g trimethylol propane 2.1 g Catalyst triethylene diamine (TEDA) 2000 ppm Material for Preventing Hydrolysis Stabaxol-1 (Carbodimide-type Material) 1.0 g Anti-Oxidant Irganox 1035 0.5 g Molding Condition 130°C for 30 minutes Secondary Molding Temperature 130°C for 4 hours The hardening agent was added to the heated and thus dissolved urethane prepolymer, and the mixed materials were injected into a heated mold so as to be heated and hardened so that a predetermined shape was formed. Physical Properties of the Obtained Member Hardness of the Rubber JISA 62, Compression Set (70°) 9% Example 2 Rubber ethylene adipate type urethane polymer (PEA) (Mn1500 manufactured by Nihon PolyUrethane, NCO 6.2 wt%) 100g Hardening Material 1,4-butandiol 3.9 g trimethylol propane 2.1 g Catalyst pentamethyl diethylene triamine (PMDETA) 2000 ppm Material for Preventing Hydrolysis Stabaxol-1 (Carbodimide-type Material) 1.0 g Anti-Oxidant Irganox 1035 0.5 g Molding Condition 130°C for 30 minutes Secondary Molding Temperature 130°C for 4 hours The hardening agent was added to the heated and thus dissolved urethane prepolymer, and the mixed materials were injected into a heated mold so as to be heated and hardened so that a predetermined shape was formed. Physical Properties of the Obtained Member Hardness of the Rubber JISA 62, Permanent Set (70°)10% Example 3 Rubber ethylene butylene adipate type urethane prepolymer (PEBA) (Mn1500 manufactured by Nihon PolyUrethane, NCO 6.2 wt%) 100g Hardening Material 1,4-butandiol 3.9 g trimethylol propane 2.1 g Catalyst triethylene diamine (TEDA) 2000 ppm Material for Preventing Hydrolysis Stabaxol-1 1.0 g Anti-Oxidant Irganox 1035 0.5 g Molding Condition 130°C for 30 minutes Secondary Molding Temperature 130°C for 4 hours The hardening agent was added to the heated and thus dissolved urethane prepolymer, and the mixed materials were injected into a heated mold so as to be heated and hardened so that a predetermined shape was formed. Physical Properties of the Obtained Member Hardness of the Rubber JISA 66, Permanent Set (70°) 12% Comparative Example 1 Rubber ethylene adipate type urethane prepolymer (PEA) (Mn1500 manufactured by Nihon PolyUrethane, NCO 6.2 wt%) 100g Hardening Material 1,4-butandiol 3.9 g trimethylol propane 2.1 g Catalyst dibutyltin dilaurate (DBTDL) 1500 ppm Material for Preventing Hydrolysis Stabaxol-1 (carbodiimide) 1.0 g Anti-Oxidant Irganox 1035 0.5 g Molding Condition 130°C for 30 minutes Secondary Molding Temperature 130°C for 4 hours The hardening agent was added to the heated and thus dissolved urethane prepolymer, and the mixed materials were injected into a heated mold so as to be heated and hardened so that a predetermined shape was formed. Physical Properties of the Obtained Member Hardness of the RubberJISA 62, Permanent Set (70°) 12% The thus manufactured urethane elastic blade was mounted on the developing unit, and then the developing unit was loaded in a laser beam printer (Lasershot manufactured by Canon) in an ambient in which the temperature was 32.5°C and the relative humidity was 90%. Then, the printing test was performed such that an image is output one time per three days for one month continuously. Results of the hydrolysis resistance test are shown in Table 1. As can be understood from the table, Examples 1 to 3 exhibited excellent capability of preventing irregular density and blooming as compared with Comparative Example 1. Thus, the superiority of the amine-type catalyst was confirmed. Example 1 Example 2 Example 3 Comparative Example 1 Polyol PEA PEA PEBA PEA Catalyst (ppm) TEDA 2000 PMDETA 2000 TEDA 2000 DBTDL 1500 Material for Preventing Hydrolysis (g) Stabaxol-1 Stabaxol-1 Stabaxol-1 Stabaxol-1 1 1 1 1 Anti-Oxidant (g) 1035 1035 1035 1035 0.5 0.5 0.5 0.5 JISA Hardness of Elastic Layer 62 62 66 62 Compression Set (%) 9 10 12 9 Test for One Month Irregular Density O O O ▵ Lines O O O O Fog O O O X Note (1) Shape of the elastic blade: 240 x 15 x 1 mm (thickness) (2) Hardness of the rubber: JISA hardness of spring confirming to JIS K6301 (3) Compression set: compressed by 25% at 70°C for 22 hours conforming to JIS K6301.

Claims: A developing unit comprising: a container (2) for containing developer (6); a developing sleeve (3) for conveying the developer, supplied from said container, to a developing position; and a regulatory member (4), of polyurethane rubber composition, in contact with the surface of said developing sleeve, for regulating the quantity of the developer conveyed on said developing sleeve to said developing position; characterised in that: said regulatory member (4) of polyurethane rubber composition contains an amine catalyst. The developing unit of claim 1, wherein said amine catalyst is at least one or triethylene diamine and pentamethyldiethylene triamine. The developing unit of claim 1 or claim 2, wherein a polyol component of said polyurethane rubber composition is polyester-type polyol. The developing unit of claim 3 wherein the polyester-type polyol is at least one of ethylene adipate type polyester polyol and ethylene butylene adipate type polyester polyol. The developing unit of any preceding claim, wherein said amine-type catalyst is at least one of triethylene diamine, and pentamethyl diethylene triamine, and said polyol component of said polyurethane rubber composition is polyester-type polyol. The developing unit of any preceding claim, wherein a material for preventing hydrolysis and an anti-oxidant are contained in said polyurethane rubber composition. The developing unit of any preceding claim including developer (6) contained by said container (2). A copying machine or a laser beam printer having: an image carrying member (1); a developing unit (2-5) for applying a developer to said image carrying member to develop the electrostatic latent image formed on said image carrying member; and characterised in that: the developing unit (2-5) is a developing unit as claimed in any of claims 1 to 7. A method of developing an electrostatic latent image on an image carrying member (1) which comprises applying developer (6) to said member (1) by means of the developing unit (2-5) of any of the preceding claims 1 to 7. A method of producing a printed image in which an electrostatic latent image is formed on the surface of an image carrying member (1), the electrostatic latent image is developed by the method of claim 9, and the developed image is transferred from the image carrying member onto a printable medium and fixed to produce the printed image.

Inventors: NIWANO KENTARO, WATABE MASAHIRO, YAMAMOTO ARIHIRO, YANAI NORIYUKI, NIWANO, KENTARO, WATABE, MASAHIRO, YAMAMOTO, ARIHIRO, YANAI, NORIYUKI, NIWANO, KENTARO, C/O CANON KABUSHIKI KAISHA, WATABE, MASAHIRO, C/O CANON KABUSHIKI KAISHA, YAMAMOTO, ARIHIRO, C/O CANON KABUSHIKI KAISHA, YANAI, NORIYUKI, C/O CANON KABUSHIKI KAISHA
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1994
Main classification: C08G18
IPC codes: G03G15, C08G18